NO127966B - - Google Patents
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- NO127966B NO127966B NO01825/70A NO182570A NO127966B NO 127966 B NO127966 B NO 127966B NO 01825/70 A NO01825/70 A NO 01825/70A NO 182570 A NO182570 A NO 182570A NO 127966 B NO127966 B NO 127966B
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- Prior art keywords
- group
- cobalt
- sulfonic acid
- dyes
- azo
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- 239000000975 dye Substances 0.000 claims description 40
- 239000010941 cobalt Substances 0.000 claims description 20
- 229910017052 cobalt Inorganic materials 0.000 claims description 20
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 18
- NYGZLYXAPMMJTE-UHFFFAOYSA-M metanil yellow Chemical group [Na+].[O-]S(=O)(=O)C1=CC=CC(N=NC=2C=CC(NC=3C=CC=CC=3)=CC=2)=C1 NYGZLYXAPMMJTE-UHFFFAOYSA-M 0.000 claims description 17
- 125000000542 sulfonic acid group Chemical group 0.000 claims description 12
- 125000000751 azo group Chemical group [*]N=N[*] 0.000 claims description 10
- 239000003795 chemical substances by application Substances 0.000 claims description 10
- 239000002253 acid Substances 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 5
- 150000003839 salts Chemical class 0.000 claims description 5
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical group OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 4
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 claims description 4
- 239000000987 azo dye Substances 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 125000001624 naphthyl group Chemical group 0.000 claims description 3
- 125000001820 oxy group Chemical group [*:1]O[*:2] 0.000 claims description 3
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical group OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims 1
- 229910052782 aluminium Inorganic materials 0.000 description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 8
- 150000001869 cobalt compounds Chemical class 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-N acetic acid Substances CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 4
- -1 cobalt tetramine sulphates Chemical class 0.000 description 4
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 230000008878 coupling Effects 0.000 description 4
- 238000010168 coupling process Methods 0.000 description 4
- 238000005859 coupling reaction Methods 0.000 description 4
- 238000001465 metallisation Methods 0.000 description 4
- BDHFUVZGWQCTTF-UHFFFAOYSA-N sulfonic acid Chemical group OS(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-N 0.000 description 4
- RUFPHBVGCFYCNW-UHFFFAOYSA-N 1-naphthylamine Chemical class C1=CC=C2C(N)=CC=CC2=C1 RUFPHBVGCFYCNW-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 150000008049 diazo compounds Chemical class 0.000 description 3
- 238000004043 dyeing Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- GWIAAIUASRVOIA-UHFFFAOYSA-N 2-aminonaphthalene-1-sulfonic acid Chemical compound C1=CC=CC2=C(S(O)(=O)=O)C(N)=CC=C21 GWIAAIUASRVOIA-UHFFFAOYSA-N 0.000 description 2
- JBIJLHTVPXGSAM-UHFFFAOYSA-N 2-naphthylamine Chemical compound C1=CC=CC2=CC(N)=CC=C21 JBIJLHTVPXGSAM-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 150000001555 benzenes Chemical class 0.000 description 2
- 229940011182 cobalt acetate Drugs 0.000 description 2
- 229940044175 cobalt sulfate Drugs 0.000 description 2
- 229910000361 cobalt sulfate Inorganic materials 0.000 description 2
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 125000000664 diazo group Chemical group [N-]=[N+]=[*] 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 1
- MJWDIGUUVRCTFY-UHFFFAOYSA-N 6-methoxynaphthalen-2-amine Chemical compound C1=C(N)C=CC2=CC(OC)=CC=C21 MJWDIGUUVRCTFY-UHFFFAOYSA-N 0.000 description 1
- GSUBEKBKJCYWBJ-UHFFFAOYSA-N 6-methylnaphthalen-2-amine Chemical compound C1=C(N)C=CC2=CC(C)=CC=C21 GSUBEKBKJCYWBJ-UHFFFAOYSA-N 0.000 description 1
- FQHDMJVMCFEDCJ-UHFFFAOYSA-L C(=O)([O-])C(O)C(O)C(=O)[O-].[Co+2].[Na+] Chemical compound C(=O)([O-])C(O)C(O)C(=O)[O-].[Co+2].[Na+] FQHDMJVMCFEDCJ-UHFFFAOYSA-L 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- JGMQCCDFCFOVMF-UHFFFAOYSA-N NOC1=CC(=CC(=C1)[N+]([O-])=O)S(O)(=O)=O Chemical compound NOC1=CC(=CC(=C1)[N+]([O-])=O)S(O)(=O)=O JGMQCCDFCFOVMF-UHFFFAOYSA-N 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000001447 alkali salts Chemical class 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 150000001448 anilines Chemical class 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 239000002585 base Chemical class 0.000 description 1
- 239000000337 buffer salt Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 150000004700 cobalt complex Chemical class 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 230000009918 complex formation Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000006193 diazotization reaction Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 239000003960 organic solvent Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- HELHAJAZNSDZJO-OLXYHTOASA-L sodium L-tartrate Chemical compound [Na+].[Na+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O HELHAJAZNSDZJO-OLXYHTOASA-L 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 235000010288 sodium nitrite Nutrition 0.000 description 1
- 239000001433 sodium tartrate Substances 0.000 description 1
- 229960002167 sodium tartrate Drugs 0.000 description 1
- 235000011004 sodium tartrates Nutrition 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 229910021653 sulphate ion Inorganic materials 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/34—Simultaneous production of alkali metal hydroxides and chlorine, oxyacids or salts of chlorine, e.g. by chlor-alkali electrolysis
- C25B1/46—Simultaneous production of alkali metal hydroxides and chlorine, oxyacids or salts of chlorine, e.g. by chlor-alkali electrolysis in diaphragm cells
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C10/00—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition
- C03C10/16—Halogen containing crystalline phase
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B13/00—Diaphragms; Spacing elements
- C25B13/04—Diaphragms; Spacing elements characterised by the material
- C25B13/08—Diaphragms; Spacing elements characterised by the material based on organic materials
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
- C25B9/17—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof
- C25B9/19—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof with diaphragms
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Electrochemistry (AREA)
- Metallurgy (AREA)
- Ceramic Engineering (AREA)
- Inorganic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Glass Compositions (AREA)
- Compositions Of Oxide Ceramics (AREA)
Description
Fremgangsmåte til fremstilling av koboltholdige azo-fargestoffer. Process for the production of cobalt-containing azo dyes.
Det ble funnet at man kommer til nye, verdifulle azofargestoffer, når man lar koboltavgivende midler innvirke på sulfonsyregruppeholdige monoazofargestoffer som tilsvarer den generelle formel It was found that new, valuable azo dyes are obtained when cobalt-releasing agents act on sulfonic acid group-containing monoazo dyes corresponding to the general formula
i hvori R betyr en nitrogruppeholdig oksybenzolrest som er bundet til azogruppen i o-stilling til oksygruppen, A betyr en naftalinrest som er bundet til azogruppen i nabostilling til gruppe Y, og Y betyr en høyst sekundær aminogruppe, særlig -NH2-gruppen. De monoazofargestoffer som tilsvarer den ovenstående formel og som ved foreliggende fremgangsmåte tjener som utgangsstoffer kan fåes av o-oksydiazoforbindelser fra benzolrekken og aminonaftaliner som koples i nabostilling til aminogruppen, idet minst et av utgangsstoffene må være sulfonsyregruppeholdig. De således erholdte sulfonsyregruppeholdige utgangsmonoazofargestoffer med formel 1) kan også i resten R og/eller i resten A inneholde en sulfonsyregruppe, eller det kan være til stede to sulfonsyregrupper i resten A mens R inneholder en til to nitrogrupper eventuelt ved siden av andre substituenter som er vanlige i monoazofargestoffer, slik som halogenatomer eller alkyl-grupper. Som eksempler på o-oksydiazoforbindelser fra benzolrekken, som kan anvendes til fremstilling av de monoazofargestoffer som ved foreliggende fremgangsmåte tjener som utgangsstoffer skal nevnes slike, som kan fåes av føl-gende aminer: 4-nitro-2-amino-l-oksybenzol-6-sulfonsyre, 6-nitro-2-amino-oksybenzol-4-sulfonsyre, videre sulfonsyregruppefrie diazokomponenter, som bare skal koples med en sulfonsyregruppeholdig natylamin slik som de diazoforbindelser som kan fåes av in which R means an oxybenzene residue containing a nitro group which is bound to the azo group in the o-position to the oxy group, A means a naphthalene residue which is bound to the azo group in a neighboring position to group Y, and Y means a highly secondary amino group, especially the -NH2 group. The monoazo dyes which correspond to the above formula and which in the present method serve as starting materials can be obtained from o-oxydiazo compounds from the benzene series and aminonaphthalenes which are coupled in a neighboring position to the amino group, as at least one of the starting materials must contain a sulfonic acid group. The sulfonic acid group-containing starting monoazo dyes with formula 1) thus obtained may also contain a sulfonic acid group in the residue R and/or in the residue A, or two sulfonic acid groups may be present in the residue A while R contains one to two nitro groups, possibly next to other substituents which are common in monoazo dyes, such as halogen atoms or alkyl groups. As examples of o-oxydiazo compounds from the benzene series, which can be used for the production of the monoazo dyes which in the present process serve as starting materials, those which can be obtained from the following amines should be mentioned: 4-nitro-2-amino-1-oxybenzene-6 -sulfonic acid, 6-nitro-2-amino-oxybenzene-4-sulfonic acid, further sulfonic acid group-free diazo components, which must only be coupled with a sulfonic acid group-containing natylamine such as the diazo compounds that can be obtained from
4- nitro-2-amino-l-oksybenzol, 5- nitro-2-amino-l-oksybenzol, 4-klor-5-nitro-2-amino-l-oksybenzol, 4-metyl-5-nitro-2-amino-l-oksybenzol, 4-nitro-6-klor-2-amino-l-oksybenzol, 4-nitro-6-acetylamino-2-amino-l-oksybenzol, 6- nitro-4-acetylamino-2-amino-l-oksybenzol, 6-nitro-4-metyl-2-amino-l-oksybenzol, 6-ntiro-4-klor-2-amino-l-oksybenzol, 4,6-dinitro-2-amino-l-oksybenzol. 4-nitro-2-amino-l-oxybenzene, 5-nitro-2-amino-l-oxybenzene, 4-chloro-5-nitro-2-amino-l-oxybenzene, 4-methyl-5-nitro-2- amino-l-oxybenzene, 4-nitro-6-chloro-2-amino-l-oxybenzene, 4-nitro-6-acetylamino-2-amino-l-oxybenzene, 6-nitro-4-acetylamino-2-amino- l-oxybenzene, 6-nitro-4-methyl-2-amino-l-oxybenzene, 6-nitro-4-chloro-2-amino-l-oxybenzene, 4,6-dinitro-2-amino-l-oxybenzene.
Som azokomponenter kommer i betraktning aminonaftalinforbindelser som kopler i nabostilling til en primær eller sekundær aminogruppe, og som kan inneholde sulfonsyregrupper. Anvender man sulfonsyregruppeholdige diazokomponenter, kan man kople med sulfonsyregruppefrie aminonaftalinforbindelser, slik som 6-brom- eller 6-metoksy-2-aminonaftalin, 6-metyl-2-amino-naftalin og fremfor alt 2-aminonaftalin selv. I stedet for disse siste komponenter kan man også anvende 2-aminonaftalin-l-sulfonsyre, da denne syre som be-kjent kopler i 1-stilling under avspaltning av sulfonsyregruppen og derfor fører til de samme utgangsfargestoffer som 2-aminonaftalinet selv. Videre kommer i betraktning som koplings-komponenter aminonaftalinsulfonsyrer, som kan kombineres med de angitte sulfonsyregruppefrie diazoforbindelser. Som slike kan man nevne: 2-i'enylaminonaftalin-2'-, -3'- eller -4'- sulfonsyre, l-aminonaftalin-4- eller -5-sulfonsyre, 2-aminonaftalin-4-, -5-, -6- eller -7-sulfonsyre, 2-aminonaftalin-3,6- eller 4,7-disulfonsyre. As azo components, aminonaphthalene compounds which connect in a neighboring position to a primary or secondary amino group, and which may contain sulfonic acid groups, come into consideration. If diazo components containing sulphonic acid groups are used, it is possible to couple with sulphonic acid group-free aminonaphthalene compounds, such as 6-bromo- or 6-methoxy-2-aminonaphthalene, 6-methyl-2-amino-naphthalene and above all 2-aminonaphthalene itself. Instead of these last components, 2-aminonaphthalene-1-sulfonic acid can also be used, as this acid as is known couples in the 1-position during cleavage of the sulfonic acid group and therefore leads to the same starting dyes as 2-aminonaphthalene itself. Furthermore, aminonaphthalene sulfonic acids, which can be combined with the specified sulfonic acid group-free diazo compounds, are also considered as coupling components. As such one can mention: 2-enylaminonaphthalene-2'-, -3'- or -4'-sulfonic acid, 1-aminonaphthalene-4- or -5-sulfonic acid, 2-aminonaphthalene-4-, -5-, -6- or -7-sulfonic acid, 2-aminonaphthalene-3,6- or 4,7-disulfonic acid.
Koplingen av de diazoforbindelser som fåes av de ovenfor nevnte aminobenzoler på vanlig måte, f. eks. ved hjelp av natriumnitritt og saltsyre med de azokomponenter som kommer i betraktning kan likeledes foregå på vanlig måte, f. eks. i nøytralt til surt miljø. The coupling of the diazo compounds obtained from the above-mentioned aminobenzenes in the usual way, e.g. with the help of sodium nitrite and hydrochloric acid with the azo components that come into consideration can likewise take place in the usual way, e.g. in a neutral to acidic environment.
Overføringen av fargestoffene til koboltforbindelser ifølge oppfinnelsen kan skje med fargestoffer, slik som de foreligger i koplings-blandingen. Den kan også skje med det filtrerte eller med det fargestoff som er renset ved om-krystallisasjon. The transfer of the dyes to cobalt compounds according to the invention can take place with dyes, as they are present in the coupling mixture. It can also occur with the filtered or with the dye that has been purified by recrystallization.
Som koboltavgivende middel anvendes for-trinsvis salter som inneholder kobolt som kation, slik som f. eks. koboltacetat eller koboltsulfat. I mange tilfelle er anvendelsen av komplekse mtallforbindelser av fordel, f. eks. i form av metall-amin-komplekser, slik som kobolttetra-minsulfater av ammoniakk, pyridin eller mono-etanolamin, eller også i form av forbindelser som inneholder kobolt komplekset bundet i anionet, f. eks. komplekse koboltforbindelser av alkalisalter av alifatiske aminokarbonsyrer eller oksykarbonsyrer, f. eks. av glykokol, melkesyre og fremfor alt av vinsyre, slik som natrium-kobolttartrat. Salts that contain cobalt as a cation are preferably used as cobalt-releasing agents, such as e.g. cobalt acetate or cobalt sulfate. In many cases the use of complex mtal compounds is advantageous, e.g. in the form of metal-amine complexes, such as cobalt tetramine sulphates of ammonia, pyridine or mono-ethanolamine, or also in the form of compounds containing the cobalt complex bound in the anion, e.g. complex cobalt compounds of alkali salts of aliphatic aminocarboxylic acids or oxycarboxylic acids, e.g. of glycocol, lactic acid, and above all of tartaric acid, such as sodium cobalt tartrate.
Behandlingen av de monoazofargestoffer som fåes ifølge de ovenstående foregår med koboltavgivende midler ifølge foreliggende fremgangsmåte hensiktsmessig i svakt surt, nøytralt eller særlig alkalisk miljø. Det anbefales i almin-nelighet på et molekyl av et fargestoff å anvende mindre enn et atom kobolt. The treatment of the monoazo dyes obtained according to the above takes place with cobalt-releasing agents according to the present method, suitably in a weakly acidic, neutral or particularly alkaline environment. It is generally recommended to use less than one atom of cobalt per molecule of a dye.
Behandlingen med de koboltavgivende midler kan foregå etter i og for seg kjente fremgangs-måter, f. eks. ved hjelp av oppvarmning til temperaturer mellom 50 og 120° C i åpent kar, f. eks. under tilbakeløpskjøling eller eventuelt i lukket kar under trykk, idet pH-forholdene er gitt ved naturen av den valgte metalliserings-fremgangsmåte■ Således kan man f. eks. foreta en sur koboltering med koboltsulfat, en alkalisk koboltering med natriumtartrat og koboltacetat. Om ønskes kan det ved metalliseringen tilsettes videre stoffer, f. eks. salter av organiske syrer, baser, organiske oppløsningsmidler, slik som alkohol, eller videre midler som befordrer kom-pleksdannelsen. Med hensyn til valget av metall-iseringsfremgangsmåtene er det som regel til-strekkelig ved de fargestoffer som her kommer på tale med en kortere behandlingstid ved en temperatur på 70 til 90 ° C med salter, slik som acetater eller sulfater. The treatment with the cobalt-releasing agents can take place according to procedures known per se, e.g. by means of heating to temperatures between 50 and 120° C in an open vessel, e.g. under reflux cooling or possibly in a closed vessel under pressure, as the pH conditions are given by the nature of the selected metallization method■ Thus, one can e.g. carry out an acid cobaltation with cobalt sulphate, an alkaline cobaltation with sodium tartrate and cobalt acetate. If desired, further substances can be added during the metallization, e.g. salts of organic acids, bases, organic solvents, such as alcohol, or other agents which promote complex formation. With regard to the choice of the metallization methods, it is usually sufficient for the dyes in question here to have a shorter treatment time at a temperature of 70 to 90°C with salts, such as acetates or sulfates.
Et ensartet fargestoff av den til å begynne med angitte formel (1) kan f. eks. underkastes slike ovenfor forklarte metalliseringsfremgangs-måter. Det er imidlertid også mulig å metallisere på tilsvarende måte en blanding av forskjellige metalliserbare monoazofargestoffer av den til å begynne med angitte formel (1). A uniform dye of the initially stated formula (1) can e.g. are subjected to such above-explained metallization procedures. However, it is also possible to metallize in a similar way a mixture of different metallizable monoazo dyes of the initially stated formula (1).
De nye produkter som kan fåes ifølge foreliggende fremgangsmåte er komplekse koboltforbindelser av sulfonsyregruppeholdige monoazofargestoffer, som inneholder et atom kobolt komplekst bundet til to monoazofargestofF-molekyler. De er nye og er komplekse koboltforbindelser av monoazofargestoffer med forme-len The new products that can be obtained according to the present method are complex cobalt compounds of sulfonic acid group-containing monoazo dyes, which contain a cobalt atom complexly bound to two monoazo dye F molecules. They are new and are complex cobalt compounds of monoazo dyes with the formula
hvori R betyr en nitrogruppeholdig oksybenzolrest, som er bundet til azogruppen i o-stilling til oksygryppen, Y betyr en høyst sekundær aminogruppe og A betyr en naftalinrest, som er bundet til azogruppen i nabostilling til gruppen Y og idet fargestoffmolekylet inneholder minst en sulfonsyregruppe. in which R means an oxybenzene residue containing a nitro group, which is attached to the azo group in the o-position to the oxygrip, Y means a highly secondary amino group and A means a naphthalene residue, which is attached to the azo group in a neighboring position to the group Y and the dye molecule contains at least one sulfonic acid group.
Disse nye produkter fåes også når i stedet for de o-oksy-o'-aminomonoazofargestoffer som tilsvarer den generelle formel (1) de tilsvarende o-alkoksy- eller o-acyloksy-o'-aminomonoazo-fargestoffer behandles med de angitte koboltavgivende midler under slike betingelser at alkyl- henholdsvis acylgruppen i o-alkoksy-henholdsvis o-acyloksy-o'-aminoazogrupperingen avspaltes. These new products are also obtained when instead of the o-oxy-o'-aminomonoazo dyes corresponding to the general formula (1) the corresponding o-alkyloxy or o-acyloxy-o'-aminomonoazo dyes are treated with the specified cobalt releasing agents under such conditions that the alkyl or the acyl group in the o-alkoxy-respectively o-acyloxy-o'-aminoazo grouping is split off.
De nye koboltholdige fargestoffer er godt oppløselige i vann. De egner seg til fargning av de forskjelligste stoffer, fremfor alt til fargning av anodisk oksydert aluminium av vandige bad. Dette kan f. eks. skje således at man farger i et fargebad med vandige oppløsninger, som inneholder koboltforbindelsene av monoazofarge-stoffene med den generelle formel (1). Fargebadet kan samtidig med den anvendte metall-forbindelse også inneholde salter, f. eks. puffer-salter eller andre tilsetninger, som innvirker på pH-verdien og dermed på fargestoffets påtrekk-ingsevne. F. eks. kan fargebadet ved hjelp av natriumacetat og eddiksyre bringes på en pH-verdi på ca. 5 til ca. 7. The new cobalt-containing dyes are well soluble in water. They are suitable for dyeing a wide variety of substances, above all for dyeing anodically oxidized aluminum from aqueous baths. This can e.g. happen so that one dyes in a dye bath with aqueous solutions, which contain the cobalt compounds of the monoazo dyes with the general formula (1). At the same time as the metal compound used, the dye bath can also contain salts, e.g. buffer salts or other additives, which affect the pH value and thus the dye's ability to attract. For example the dye bath can be brought to a pH value of approx. 5 to approx. 7.
Etter fargningen gjøres det fargede aluminium ferdig, slik som vanlig, f. eks. ved hjelp av den kjente Sealing-operation. After coloring, the colored aluminum is finished, as usual, e.g. by means of the known Sealing operation.
Ifølge foreliggende fremgangsmåte får man på anodisk oksydert aluminium og på dets legeringer som med hensyn til anodisk oksyda-sjon forholder seg på liknende måte som aluminium, meget verdifulle fargninger, som som regel utmerker seg med meget gode vær- og lysekthet. According to the present method, very valuable colors are obtained on anodically oxidized aluminum and on its alloys, which with regard to anodic oxidation behave in a similar way to aluminum, which are usually characterized by very good weather and light fastness.
I de følgende eksempler betyr delene, så-fremt intet annet angis, vektsdeler, prosentene vektsprosenter og temperaturene er angitt i Celsiusgrader. In the following examples, unless otherwise stated, the parts mean parts by weight, the percentages are percentages by weight and the temperatures are given in degrees Celsius.
Eksempel 1. Example 1.
43,3 deler (0,1 mol) av det fargestoff som fåes ved diazotering av 4,6-dinitro-2-amino-l-oksybenzol og kopling med l-aminonaftalin-4-sulfonsyre, utrøres homogent i form av en ca. 30 %'ig pasta med 1000 deler varmt vann. Etter tilsetning av 100 volumdeler 2n-natrium-hydroksydoppløsning innstilles temperaturen i blandingen på 75° C. Fargestoffet er bare delvis oppløst. Denne suspensjon tilsettes en oppløs-ning av 16,9 deler krystallisert koboltsulfat (0,06 mol) i 50 deler varmt vann. Etter kort tid er fargestoffet fullstendig oppløst. Reaksjons-blandingen omrøres i en time ved 75 til 80° C. Det koboltholdige fargestoff utskilles fra sin oppløsning ved tilsetning av 100 volumdeler 2n-eddiksyre og 100 deler natriumklorid, fra-filtreres og tørkes. Det farger anodisk oksydert aluminium etter det som er angitt i eksempel 2 i meget lysekte dypsorte nyanser. 43.3 parts (0.1 mol) of the dye obtained by diazotization of 4,6-dinitro-2-amino-l-oxybenzene and coupling with l-aminonaphthalene-4-sulfonic acid are stirred homogeneously in the form of an approx. 30% paste with 1000 parts hot water. After adding 100 parts by volume of 2n sodium hydroxide solution, the temperature in the mixture is set to 75° C. The dye is only partially dissolved. A solution of 16.9 parts of crystallized cobalt sulphate (0.06 mol) in 50 parts of warm water is added to this suspension. After a short time, the dye is completely dissolved. The reaction mixture is stirred for one hour at 75 to 80° C. The cobalt-containing dye is separated from its solution by the addition of 100 parts by volume of 2n-acetic acid and 100 parts of sodium chloride, filtered off and dried. It colors anodically oxidized aluminum according to what is indicated in example 2 in very lightfast deep black shades.
Når man i stedet for den i ovenstående eksempel angitte koboltforbindelse anvender de koboltholdige fargestoffer som fåes av de i følgende tabell angitte komponenter i kolonnene II og III og koboltsulfat, fåes ved fargning av anodisk oksydert aluminium etter det som er angitt i eksempel 2 de i kolonne IV nevnte fargenyanser. When, instead of the cobalt compound specified in the above example, the cobalt-containing dyes obtained from the components specified in the following table in columns II and III and cobalt sulfate are used, by dyeing anodically oxidized aluminum according to what is specified in example 2, those in column IV mentioned color shades.
Eksempel 2. Example 2.
En gjenstand av rent aluminium oksyderes anodisk med et vandig bad, som pr. liter inneholder 200 g vannfri svovelsyre og 10 g aluminium som sulfat, i en time ved 18 til 20° C bg ved en strømtetthet på 1,5 ampére/dm". Gjenstanden skylles grundig med kaldt vann og farges deretter i et vandig fargebad som pr. liter inneholder 8 g krystallisert natriumacetat, 1 cm<3 >40 %'ig eddiksyre og 10 g av det i eksempel 1 nevnte koboltholdige fargestoff, i 30 minutter ved 65 ° C. Den fargede gjenstand skylles grundig med kaldt vann og deretter etter-fortettes i destillert vann i 40 minutter ved 98 til 100° C. Det er farget i meget lysekte og værfaste, dyp-svarte nyanser. An object made of pure aluminum is anodically oxidized with an aqueous bath, which per liter contains 200 g of anhydrous sulfuric acid and 10 g of aluminum as sulphate, for one hour at 18 to 20° C bg at a current density of 1.5 ampere/dm". The object is thoroughly rinsed with cold water and then dyed in an aqueous dye bath as per . liter contains 8 g of crystallized sodium acetate, 1 cm<3 >40% acetic acid and 10 g of the cobalt-containing dye mentioned in example 1, for 30 minutes at 65 ° C. The colored object is rinsed thoroughly with cold water and then after is condensed in distilled water for 40 minutes at 98 to 100° C. It is dyed in very lightfast and weatherproof, deep black shades.
Claims (8)
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FR6915707A FR2044288A5 (en) | 1969-05-14 | 1969-05-14 |
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CA (1) | CA951334A (en) |
CH (1) | CH530345A (en) |
DE (1) | DE2023717A1 (en) |
ES (1) | ES379634A1 (en) |
FR (1) | FR2044288A5 (en) |
GB (1) | GB1307303A (en) |
LU (1) | LU60913A1 (en) |
NL (1) | NL7006899A (en) |
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AT390427B (en) * | 1982-07-30 | 1990-05-10 | Mo Khim T I Im Mendeleeva | GLASS CRYSTALINE MATERIAL AND METHOD FOR THE PRODUCTION THEREOF |
US4467039A (en) * | 1983-05-09 | 1984-08-21 | Corning Glass Works | Potassium fluorrichterite glass ceramics and method |
US4608348A (en) * | 1985-11-04 | 1986-08-26 | Corning Glass Works | Glass-ceramics containing cristobalite and potassium fluorrichterite |
US5250474A (en) * | 1991-02-07 | 1993-10-05 | Schott Glaswerke | Glass powder which is crystallizable to yield a sintered glass ceramic containing hexagonal cordierite as the principal crystalline phase |
DE4103778C1 (en) * | 1991-02-08 | 1992-05-14 | Schott Glaswerke, 6500 Mainz, De | |
GB2437796B (en) * | 2006-05-05 | 2011-08-03 | John William Carson | Improved blast furnace slag |
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1969
- 1969-05-14 FR FR6915707A patent/FR2044288A5/fr not_active Expired
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1970
- 1970-05-06 GB GB2174870A patent/GB1307303A/en not_active Expired
- 1970-05-12 SE SE06480/70A patent/SE361464B/xx unknown
- 1970-05-13 BE BE750369D patent/BE750369A/en unknown
- 1970-05-13 NL NL7006899A patent/NL7006899A/ not_active Application Discontinuation
- 1970-05-13 CH CH711470A patent/CH530345A/en not_active IP Right Cessation
- 1970-05-13 LU LU60913D patent/LU60913A1/xx unknown
- 1970-05-13 NO NO01825/70A patent/NO127966B/no unknown
- 1970-05-13 ES ES379634A patent/ES379634A1/en not_active Expired
- 1970-05-14 CA CA082,773,A patent/CA951334A/en not_active Expired
- 1970-05-14 DE DE19702023717 patent/DE2023717A1/en active Pending
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FR2044288A5 (en) | 1971-02-19 |
NL7006899A (en) | 1970-11-17 |
GB1307303A (en) | 1973-02-21 |
DE2023717A1 (en) | 1970-11-19 |
ES379634A1 (en) | 1973-01-16 |
CH530345A (en) | 1972-11-15 |
SE361464B (en) | 1973-11-05 |
LU60913A1 (en) | 1971-06-29 |
CA951334A (en) | 1974-07-16 |
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